Monoazo dyestuffs insoluble in water



Patented Jan. 20, 1942 UNITED STATES PATENT" OFFICE MoNoAIzo DYEs'rUFss matters; In

, WATER Ernst Fischer, offenbachaoii-theeMai'li, Germany, a ssignor to General: Aniline &' Film (lorpor'ajtion, a corporation of Delaware No Drawing: -Appliation September 15, 1939, Serial No; 295,051". In Germany September 15, 1938 5 Ciihiil The present invention relates to mono' azo dyestufis insoluble in water; more particularly, it

relates to dyestufis of the following gee-em fory C4Ho wherein the benzene radical a contains at least one alkoxy, aralkoxy or aryloxy group andriiay contain further substituents, with a 2.3'-hyd roi y-" naphthoylaminobenzene which may containa's a substituent in the hydr'oxynaphthoyl radical a halogen atom or an-alkoxy group and containsin the benzene radical at'most two further substituents, as for instance, alkyl, alkoxy, aralkoxy, aryle oxy, nitro-groups or halogen atoms, only such dyestufi components being used as'donotcontainanygroup lending solubility in; water, 1' for in: stallfi b-a sulphonio acid or carboxylic acidf group;

'Ijhe new dyestufis are insoluble in water, but very easily soluble in many organic'solvents, as for instance, hydrocarbons; alcohols, esters, ketones and, therefore, can be used for colouring these solvents as wellas thelacquers prepared by means; o i'thesesolvents, such as nitroor acetylcelluloselacquers,- films orplas tic masses. 7 They are also very suitable for colouringvarnishes,

candles and fats, Owing to the" fferent-11 sftituents present in the dyestufis the suitability of the organic solvents named varies, but the most suitable solvents may easily be ascertained by ex- 5 periment. o H

In comparison with the dyestuffs described in German patents, Nos. 480,814, 575,216, l 582,277 and 587,652, the dyestufis obtainable by the pres ent invention are distinguished by their enhanced l0 solubility in organic solvents so that they are very suitable for colouringsubstances of the aforesaid lt ini'whereas the dyestuffs of the said patents have either no solubility in organic solvents or a solubilitytoo small for these purposes, I i

The following examples serve to illustrate the invention, butthey are not intended to limit/it thereto, the parts'bing by weight: t,

i (1) 31.4-parts of1-amino-2metho;;ybenaene- 5-(sulphonyl-n:dibutylamine) are, diazo "sed in 20 the usualrnanner, Thereupon sodium'acfetateis added to the dia'zo so lution inorder to bind the mineral acid" in excess and the diazo so'lution; is

then stirred into a solution of 2,913 .pairtsofv 2,3-

xy aphth rlrfir-e n :g w b 5 acne) in dilute caustic soda solution; When the coupling is complete, the dyestuff obtained is filtered with suction, washediw'ell and dried. It is a, red powder which dissolves easi1y, i "butyl acetate, acetone, xylene and other organic sol- 0 vents and colours cellulose ester lacquers; red

tints of good fastness to light. The dyestuff corresponds with the following formula:

(2) 32.8 parts of 1-amino-4-ethoXybenzene-5- (s'ulphonyl-n-dibutyl amine) are dia'zotised in the usualmanner. 50 beeri'niade'nuetraltoCongo paper by means of The diazd-solution which has sodium" acetate'is stirred into a solution of 26.3

parts of 2.3-hydroxynaphthoyl-aminobenzene in dilute caustic soda solution. The dyestufi obtained is filtered with suction, washed well and. dried. It dissolves easily in butyl alcohol, ethyl acetate and other organic solvents and colours nitrocellulose and acetyl cellulose lacquers as well as varnishes red tints of good properties of fast ness.

(3) If there are used, in Example 1, instead of 31.4 parts of 1-amino-2-methoxybenzene-5-(sulphonyl-n-dibutylamine) 34.4 parts of l-amino- 2.5-dimethozqrbenzene-4-(sulphonyl n dibutylamine), a dyestuff of similarly good properties of fastness is obtained; it colours the various organic solvents and the lacquers prepared therewith as well as candles and fats Bordeaux-red tints.

The following table indicates a number of other mono-azo-dyestuffs obtainable by this invention, which are likewise easily soluble in the solvents suitable for these purposes and have good properties of fastness.

wherein X stands for a member of the group consisting of hydrogen, alkoxy and halogen, Y1

stands for a member of the group consisting of Dram-compound from Coupled with- Shade 2.3-hydroxynaphthoyl- 1 1 ammo 2 methoxybenzene 5 (sulphonyl n Aminobenzene Red.

dibutylamine) 2 do (1'-amino-3'-methyl-4-metboxybenzene). Red. 3 E1'-ammo-2-methoxybenzene) Red. 4 do 1'-am1no-2.4-dimethylbenzene) Red. 5 1 ammo- 4 methoxybenzene 5 (sulphonyl n (1 -a.mino-4-methoxybenzene) Red.

dibutylamine).

d (1-amino-2-ethoxybenzene) Red. (1-am no-3-nitrobenzene) Red. (l-am no-4-chlorobenzene Red. (l-am no-4'-methylbenzene) Red. (1-amrno-2-methoxy-5-ch1orobenzene) Red. (l'-am no-2'-ethylbenzene) Red. (l-am1no-2'-bromobenzene) Red. (1-am1no-2-benzyloxybenzene) Red. (1-amino-2-phenoxybenzene) Red. (l-am no-4'-phenoxybenzene). Red. (4-ammo-di pheny Red. (4-amino-1 2", 3", 4", 5'2 6-hexahydro- Red.

diphenyl). 18 do. l (4-ammo-l", 2", 3", 4-tetrahydrodiphenyl) Red. 19 1 ammo 2 e oxybenzene 5 (sulphonyl n (1-amino-2'methoxy-5'-chlorobenzene). Red.

dibutylamine) 20 do (lamino-Mmethoxybenzene) Red. 21 1 amino 2 benzyloxybenzene 5 (sulphonyl do Red.

n-dibutylamine) 22 1 amino 4 ethoxybenzene 5 (sulphonyl n do Red.

dibutyl amine) 23 1 amino 2 phenoxybenzene 5 (sulphonyl n do Red.

dibutylamine) 24 1 amino 3 methoxybenzene 5 (sulphonyl n do Rod.

dibutylamine) 25 1 amino 4 methoxybenzene G (sulphonyl n do Red.

dibutylamine) 26 1 amino 2 methoxybenzene 5 (sulphonyl do Red.

di-isobutylamine) 27 .1 -amino 2.4 dimethoxybenzene -5 (sulphonyldo Red.

n-dibutyl amine) 1 28 1 amino 2 -methoxy 4 chlorobenzene 5 -(su1 "do Red.

phonyl-n-dibutylamine). 29 1 amino 2 methoxy 5 methylbenzene 4 do Red.

(sulphonyl-n-dibutylamine) 30 1 amino 2 methoxybenzene 4 (sulphonyl n Red.

dibutylamine) 31 1 amino 2.5 dimethoxybenzene 4 (sulphonyl- Bordeaux.

n-dibutylamine). 32 do (l-amino-2.5'-dimethoxybenzene) Bordeaux. 33 1 amino 2.5 diethoxybenzene 4 (sulplionyl (1-amino-4-methoxybenzene) Bordeaux.

n-dibutylamine) 6-brom0-2.3-hydtoxynaphthoyl- 34 1-amino-2.5-dimethoxybenzene-4-(sulphonyl-n- (1'-amino-2-methyl-4-chlorobenzene) Red-violet.

dibutylamine) 35 do (1-amino-3-mtrobenzene) Red-violet.

6-methoxy-2.3-hydr0xynaphthoy1- 36 do Aminobenzene Red-violet. 37 1 amino 2 methoxybenzene 5 (sulphonyl n do Bordeaux.

dibutylamine) 1 amino 2,5 dimethoxybenzene 4 (sulphonyl- (Famine-3'-mtrobenzene) Violet.

n-dibutylamine) Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestufis are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims, do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies.

alkoxy, benzyloxy and phenoxy, Y2 for a member of the group consisting of hydrogen, alkoxy, alkyl and halogen, Z1 for a member of the group consisting of hydrogen, alkyl, alkoxy, benzyloxy, phenoxy, phenyl, hydrogenated phenyl, nitro and halogen and. Z2 for a member of the group consisting of hydrogen, alkyl and alkoxy, being insoluble in water, but very easily soluble in organic solvents and yielding red to violet shades Substituents of this kind are, for instance, the of good properties of fastness.

2. The water-insoluble mono-azo-dyestuffs of the following general formula:

N II

OH OCH;

GO.NH

S O :N

C Ho

being a red powder which dissolves easily in organic solvents, such as butyl alcohol, butyl acetate, acetone, xylene and colours, for instance, cellulose ester lacquers red tints of good fastness to light.

4. The water-insoluble mono-azo-dyestufi of the following formula:

C4Ho

SOzN (n) C4Hn N I] N O OH:

being a red powder which dissolves easily in oranic solvents, such as butyl alcohol, butyl acetate, acetone, xylene and colours, for instance, cellulose ester lacquers red tints of good properties of iastness.

5. The water-insoluble mono-azo-dyestuff of the following formula:

C4Hu

OCH:

CHaO

OH OCH:

CO.NH

being a red powder which dissolves easily in organic solvents, such as butyl alcohol, butyl acetate, acetone, xylene and colours, for instance cellulose ester lacquers as well as candles and fats Bordeaux-red tints of good properties ofv fastness.

ERNST FISCHER. 

